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WO2018106388A1 - Polyéthylènes métallocènes à large distribution orthogonale pour films - Google Patents

Polyéthylènes métallocènes à large distribution orthogonale pour films Download PDF

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Publication number
WO2018106388A1
WO2018106388A1 PCT/US2017/060433 US2017060433W WO2018106388A1 WO 2018106388 A1 WO2018106388 A1 WO 2018106388A1 US 2017060433 W US2017060433 W US 2017060433W WO 2018106388 A1 WO2018106388 A1 WO 2018106388A1
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WO
WIPO (PCT)
Prior art keywords
range
polyethylene
film
temperature
molecular weight
Prior art date
Application number
PCT/US2017/060433
Other languages
English (en)
Inventor
Matthew W. Holtcamp
Ching-Tai Lue
Adriana S. Silva
Dongming Li
David M. Fiscus
Original Assignee
Exxonmobil Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to CN201780083063.XA priority Critical patent/CN110167974B/zh
Priority to MYPI2019003171A priority patent/MY191910A/en
Priority to BR112019011558-7A priority patent/BR112019011558B1/pt
Priority to EP17798368.1A priority patent/EP3548525A1/fr
Priority to CA3045440A priority patent/CA3045440C/fr
Priority to JP2019530059A priority patent/JP7045377B2/ja
Priority to KR1020197016144A priority patent/KR102212822B1/ko
Publication of WO2018106388A1 publication Critical patent/WO2018106388A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the present disclosure relates to polyethylenes useful for films and in particular to films made from polyethylenes that have a complex multi-modality in molecular weight and short-chain branching distribution desirable for blown films.
  • a polyethylene comprising (or consisting of, or consisting essentially of) ethylene derived units and within a range from 0.5 to 20 wt% of C3 to C12 a-olefin derived units by weight of the polyethylene; the polyethylene having a density of less than 0.94 or 0.93 g/cm 3 , an h value within a range from 0.5 to 20 g/10 min; and having an value within a range from 5 to 100 g/10 min; wherein the polyethylene fractions elute from a temperature-gradient gel permeation chromatographic column at a gradient of temperatures and molecular weights, where 50 wt% or less of the cumulative molecular weight polyethylene fractions elute at a temperatures and greater than 50 wt% cumulative
  • molecular weight polyethylene fractions elute at a temperature the molecular weight fractions eluting at being a molecular weight component and the fractions eluting at
  • Tw2 being a molecular weight component wherein the M value of the
  • polyethylene is at least 0.9 measured at a Twi-Tw2 value within a range from -16 to -36°C.
  • a film comprising (or consisting of, or consisting essentially of) the polyethylene described herein, having a Dart Drop value of at least 500 g/mil, and a Gloss (MD or TD) of at least 40%.
  • Also disclosed herein is a process to form the polyethylene described herein comprising (or consisting of, or consisting essentially of) combining a bridged bis- cyclop entadi eny 1 Group 4 metal catalyst, an unbridged bis-cyclopentadienyl Group 4 metal catalyst, and an activator with ethylene and within a range from 0.1 to 5 wt% (relative to the weight of all monomers) of a C3 to C12 a-olefin at a temperature within a range from 60 to 100°C, wherein the bridged bis-cyclopentadienyl Group 4 metal catalyst is selected from catalysts represented by the following formula:
  • each R 1 to R 8 are independently selected from CI to C20 alkoxides, or CI to C20 substituted or unsubstituted alkyl groups; provided that at least one of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 is a linear C3 to CIO substituted or unsubstituted alkyl group, wherein any two of R 1 or R 2 and/or R 7 and R 8 can form an aromatic ring comprising 5 to 7 carbons; T is a bridging group; and each X is, independently, a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.
  • FIG. 1 is an 3 ⁇ 4 NMR olefinic analysis of an exemplary polyethylene from gas phase ethylene/hexene polymerization using supported mixed catalyst: Rac/meso Me 2 Si(3- nPrCp) 2 HfMe 2 : (l-EtInd) 2 ZrMe 2 : Additive: IrganoxTM 1010.
  • FIG. 2 is a graph of weight percent as a function of temperature of CFC (TREF) data, demonstrating the calculation of Twi and Tw 2 for the same polymer in FIG. 1.
  • FIG. 3 is a graph of weight average molecular weight as a function of temperature of CFC data, demonstrating the calculation of Mwi and Mw 2 for the polymer in FIG. 1.
  • FIG. 4 is a plot of Compositional Distribution (molecular weight as a function of branching) plotting (Mwi/Mw 2 ) values as a function of (Twi - Tw 2 ) for inventive and comparative polymers.
  • the lower density BOCD-type polyethylenes described herein were achieved by providing a polyethylene that is multimodal in molecular weight and short chain branching. This is accomplished by the use of a combined catalyst system wherein a poor-comonomer incorporating catalyst is combined with a high-comonomer incorporating catalyst in a gas phase process to produce the multimodal polyethylene having the desired BOCD.
  • Such polyethylenes are highly useful in forming films such as cast or blown films, especially blown films formed by melt extrusion of the polyethylene into a sheet or cylindrical/tubular form and exposed to positive air pressure against the forming film to expand the sheet in the transverse and machine directions (TD and MD), with or without some machine direction (MD) tension, stretching the material before or during cooling.
  • the inventive polyethylenes are also useful in extrusion coating applications.
  • the term "film” refers to a continuous, flat, preferably flexible, polymeric structure having an average thickness within a range from 0.1, or 1, or 10, or 15 ⁇ to 40, or 60, or 100, or 200, or 250 ⁇ , or such a coating of similar thickness adhered to a flexible, non-flexible or otherwise solid structure.
  • the "film” may comprise (or consist of) one layer, or multiple layers, each of which may comprise (or consist of, or consist essentially of) the inventive polyethylene.
  • one or more layers of a "film” may include a mixture of the polyethylene as well as a LDPE, another LLDPE, polypropylene homo- and copolymers, or a plastomer (high comonomer polyethylene).
  • a LDPE low density polyethylene
  • LLDPE low density polyethylene
  • polypropylene homo- and copolymers polypropylene homo- and copolymers
  • plastomer high comonomer polyethylene
  • films include labeling and packaging applications, desirably stretch and cling films for wrapping around articles of commerce.
  • a polyethylene comprising (or consisting of, or consisting essentially of) ethylene derived units and within a range from 0.5 to 10, or 15, or 20 wt% of C3 to C12 a-olefin derived units by weight of the polyethylene, and having a density of less than 0.94, or 0.93 g/cm 3 , an h value within a range from 0.5 to 2, or 4, or 6, or 12, or 20 g/10 min (ASTM D1238, 2.16 kg, 190°C), and an hi value within a range from 5, or 8 to 20, or 30, or 40, or 60, or 80, or 100 g/10 min (ASTM D1238, 21.6 kg, 190°C); wherein a gradient of polyethylene fractions elutes from a temperature-gradient gel permeation chromatographic column (measured by GPC and CFC techniques described below) at a gradient of temperatures, where 50 wt% or less of the cumulative molecular weight polyethylene fractions elute at
  • the polyethylene has an M w i value of greater than 150,000, or 170,000 g/mole, or within a range from 150,000, or 170,000 g/mole to 250,000 g/mole, or 280,000 g/mole, or 300,000 g/mole, or 350,000 g/mole, or 400,000 g/mole.
  • the polyethylene of any one of the previous claims has an M W 2 value is less than 150,000, or 130,000, or 120,000 g/mole, or within a range from 60,000, or 80,000 g/mole to 120,000, or 130,000 g/mole, or 140,000 g/mole.
  • the polyethylene' s multi-modality can be quantified whereby there is a difference of at least 50,000, or 80,000 g/mole in the weight average molecular weight (Mw) of the components, or a difference within the range from 50,000, or 80,000 g/mole to 100,000, or 120,000, or 160,000 g/mole.
  • both the high and low Mw components have, individually, an MWD (Mw/Mn, Mn being the number average molecular weight) within a range from 1.8, or 2 to 3.5, or 4, or 4.5, or 5.
  • the polyethylene has a level of short-chain branching on the Mw2 fractions that is greater than that for the M w i fractions.
  • This is referred to sometimes in the art as having BOCD.
  • CFC cross-fractionation chromatography
  • this is characterized in any embodiment where cross-fractionation chromatography (CFC) is performed such that polyethylene fractions elute from a temperature-gradient gel permeation chromatographic column at a gradient of temperatures and molecular weights, where 50 wt% or less of the cumulative molecular weight polyethylene fractions elute at a temperature T w i, and greater than 50 wt% cumulative molecular weight polyethylene fractions elute at a temperature T W 2, the molecular weight fractions eluting at T w i being a molecular weight component M w i and the fractions eluting at Tw2 being a molecular weight component M W 2; wherein the Mwi/Mw2 value of the polyethylene is at least
  • the polyethylene has an overall Mw as measured by gel- permeation chromatography (GPC-4D) within the range from 100,000, or 120,000 g/mole to 140,000, or 160,000, or 200,000 g/mole; and an Mn value within the range from 8,000, or 10,000 g/mole to 30,000, or 36,000 g/mole; and a z-average molecular weight (Mz) within the range from 200,000, or 220,000 g/mole to 260,000, or 300,000, or 340,000 g/mole.
  • GPC-4D gel- permeation chromatography
  • the overall Mw/Mn (MWD) of the polyethylene is within the range from 3, or 4 to 5, or 6, or 8, or 10 or 12, or 16, or 20, or 30, where an exemplary MWD range is within the range from 3 to 10.
  • the overall Mz/Mw value is within a range from 2, or 2.2, or 2.4 to 2.8, or 3, or 3.5.
  • the polyethylenes have other features as well, including a desirable level of both internal (along the polymer chain) and terminal carbon-carbon double bonds or "unsaturations".
  • the polyethylene has a total number of internal unsaturations, as measured by NMR described below, within a range from 0.1 , or 0.2 per 1000 carbons to 0.5, or 0.6, or 0.8 per 1000 carbons.
  • the polyethylene has a total number of terminal unsaturations, such as vinyl- or vinylidene- group, within a range from 0.001 , or 0.01 per 1000 carbons to 0.15, or 0.2, or 0.3, or 0.4 per 1000 carbons.
  • the total level of unsaturation in any embodiment is within a range from 0.5, or 0.6 to 0.8, or 1, or 1.2 per 1000 carbon.
  • the polyethylene has an I21/I2 ratio within a range from 18, or 20 to 30, or 35 or 40, or 80.
  • the polyethylenes have in any embodiment a density of less than 0.94, or 0.93 g/cm 3 (ASTM 1505, as described below); and in any embodiment, the polyethylene may have a density within a range from 0.91, or 0.915 to 0.92, or 0.925, or 0.93, or 0.94 g/cm 3 . Also, in any embodiment, the polyethylene has a percent (%) crystallinity by DSC of 40% or greater, or within a range from 40% to 48%, or 50%, or 52%; or a % crystallinity of 46 or greater by GDC, or within a range from 46% to 56%, or 60%, both DSC and GDC methods described further below.
  • the polyethylene' s hot tack performance is desirable. This is indicated in part by a measure of the "Temperature at 70% Cumulative Heat Flow", which is an estimate of the Hot Tack Temperature (°C) of a film made from the polyethylene.
  • the Temperature at 70% Cumulative Heat Flow which is determined by DSC as described below, is 117, or 118, or 119°C and greater, or within a range from 117, or 118, or 119°C to 128, or 130°C.
  • the polyethylene is formed by a process comprising combining a bridged bis-cyclopentadienyl Group 4 metal (preferably zirconium or hafnium) catalyst, an unbridged bis-cyclopentadienyl Group 4 metal catalyst, and an activator with ethylene and within a range from 0.1 to 5 wt% (relative to the weight of all monomers) of a C3 to C12 a- olefin at a temperature within a range from 60 to 100°C, wherein at least the activator and one of the catalysts is supported, most preferably all three are supported by a solid support material. This is described further below.
  • any embodiment is a process to form the polyethylene comprising (or consisting of, or consisting essentially of) combining a bridged bis-cyclopentadienyl Group 4 metal catalyst, an unbridged bis-cyclopentadienyl Group 4 metal catalyst, and an activator with ethylene and within a range from 0.1 to 5 wt%, or 0.01 to 1, or 1.5, or 2 mole% (relative to the weight/moles of all monomers) of a C3 to C8, or CIO, or C12 a-olefin (preferably 1- butene, 1-hexene, and/or 1-octene) at a temperature within a range from 60, or 50 to 80°C, or 100°C, wherein the bridged bis-cyclopentadienyl Group 4 metal catalyst is selected from catalysts represented by the following formula:
  • M is a Group 4 (of the Periodic Table of Elements) metal, preferably zirconium or hafnium, and each R 1 to R 8 are independently selected from C I to C8, or C IO, or C20 alkoxides, or CI to C8, or CI O, or C20 substituted or unsubstituted alkyl groups; provided that at least one of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 is a linear C3 to C6, or C IO substituted or unsubstituted alkyl group, wherein any two of R 1 or R 2 and/or R 7 and R 8 can form an aromatic ring comprising 5 to 7 carbons, preferably forming an indenyl ring with the cyclopentadienyl;
  • T is a bridging group, preferably a di-substituted carbon or silicon, most preferably a di-substituted silyl group such as di -phenyl or di-Cl to C4, or C6, or C IO alkyl; and
  • each X is, independently, a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; preferably each X is a halogen, most preferably a chloride of fluoride, or a C I to C5, or CI O alkyl group, most preferably methyl.
  • the bridged bis-cyclopentadienyl hafnocene catalyst is selected from structures above wherein "T" is a di-Cl to C5 alkyl or di -phenyl substituted silyl group and each of R 1 to R 8 is independently a CI to C5 alkyl.
  • the "unbridged bis-cyclopentadienyl Group 4 metal catalyst” can be any bis- cyclopentadienyl Group 4 metal compound, preferably zirconium or hafnium, most preferably zirconium. Each cyclopentadienyl can be substituted in any one, two, three or more positions along the ring with C I to C6, or C8, or C IO alkyl or alkoxy groups. As in the bridged compound above, the unbridged bis-cyclopentadienyl Group 4 metal catalyst comprises one, two or more "X" groups as defined above.
  • either one or both of the cyclopentadienyl groups in either the bridged or unbridged catalyst can be an indenyl, fluorenyl, or tetrahydroindenyl group.
  • the two "metallocene" catalysts used in the inventive process can be used in any ratio with respect to one another.
  • the bridged bis-cyclopentadienyl Group 4 metal (preferably zirconium or hafnium) catalyst is present within a range from 50, or 60 to 75 wt%, or 85 wt% by weight of the two catalysts
  • the unbridged bis- cyclopentadienyl Group 4 metal catalyst is present within a range from 50, or 40 to 25 wt%, or 15 wt% by weight of the two catalysts.
  • the metallocene catalysts also comprise (or consists essentially of, or consists of) an activator.
  • the activator is contacted with the catalyst prior to entering the polymerization reactor or concurrently while the catalyst is in the polymerization reactor being contacted by olefin monomers.
  • the "activator" comprises any compound capable of converting the catalyst precursor into an active polymerization catalyst, and preferably includes alkyl alumoxane compounds (e.g., methylalumoxane) and/or tetra (perfluorinated aromatic)borates, but more preferably comprises tetra(perfluorinated aromatic)borates.
  • the activator comprises anions selected from tetra(pentafluorophenyl)borate, tetra(perfluorobiphenyl)borate, tetra(perfluoronaphthyl)borate, and combinations thereof.
  • the activator also comprises a bulky organic cation (trialkyl ammonium, trialkylmethyl), preferably dialkylanilinium cation, or triphenylmethyl cation.
  • the activator is an alumoxane compound, preferably supported on a solid support.
  • the supported catalyst consists essentially of (or consists of) the support, activator, and at least one of the catalysts disclosed herein, preferably both catalysts and the activator.
  • the heterogeneous catalysts and activator are "associated with" an insoluble, solid support material, meaning that the catalyst and/or activator may be chemically bound to, or physically absorbed onto and/or in the support.
  • the support is selected from the group consisting of Groups 2, 4, 13, and 14 metal oxides and mixtures thereof.
  • the support is selected from the group consisting of silica, alumina, magnesia, titania, zirconia, and the like, and mixtures thereof; and is most preferably silica.
  • the support has an average surface area of from 200, or 400 to 800, or 1000, or 1200, or 1400 m 2 /g.
  • the support preferably comprises silica, for example, amorphous silica, which may include a hydrated surface presenting hydroxyl or other groups which can be deprotonated to form reactive sites to anchor activators and/or catalyst precursors.
  • Other porous support materials may optionally be present with the silica as a co-support, for example, talc, other inorganic oxides, zeolites, clays, organoclays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • Silicas that may be suitable are commercially available under the trade designations PD 14024 (PQ Corporation), D70-120A (Asahi Glass Co., Ltd. or AGC Chemicals Americas, Inc.), and the like.
  • the silica support (in unaltered form) comprises at least 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, 98 wt%, or 99 wt% or more of silica.
  • the silica support may comprise up to 5 wt%, 10 wt%, 20 wt%, 30 wt%, or 40 wt% of another compound.
  • the other compound may be any other support material discussed herein.
  • the other compound may be a titanium, aluminum, boron, magnesium, or mixtures thereof.
  • the other compound may be a talc, other inorganic oxide, zeolite, clay, organoclay, or mixtures thereof.
  • the silica support may also not include any substantial amount of any other compound, that is, the silica support may comprise less than 5 wt%, 1 wt%, 0.5 wt%, 0.2 wt%, or less of any other compound.
  • the support is preferably dry, that is, free of absorbed water. Drying of the support may be effected by heating or calcining to at least 130°C, or preferably within a range from 130 to 850°C, or 200 to 600°C, for a time of 1 minute to 100 hours, or more preferably from 12 hours to 72 hours, or from 24 hours to 60 hours.
  • the calcined support material may comprise at least some groups reactive with an organometallic compound, for example, reactive hydroxyl (OH) groups to produce the supported catalyst systems of this invention.
  • the polyethylene can be produced in any known process such as a slurry (in solution) process, such as in so-called "loop" reactors that are well known in the art, or in a gas phase reactor, especially a fluidized bed gas phase reactor wherein monomer and other gases are recirculated through a bed of polymer.
  • a gas phase reactor especially a fluidized bed gas phase reactor wherein monomer and other gases are recirculated through a bed of polymer.
  • the polyethylene is produced in a gas phase process at a gas velocity of at least 2, or 3, or 4 ft/s.
  • Such processes are well known in the art and the process for making the polyethylene is not otherwise particularly limited.
  • the polyethylene is produced in a single-reactor process, wherein the monomers contact the catalysts in only one reactor to produce the polyethylene, or a dual-reactor process where the monomers contact the catalysts in two or more reactors in parallel or series, but most preferably a single-reactor process.
  • a film comprising (or consisting of, or consisting essentially of) the polyethylene of any one of the previous claims; having a Dart Drop value of at least 500, or 550, or 600 g/mil, or within a range from 500, or 550, or 600 to 700 g/mil, or 800 g/mil or 1000 g/mil, and a Gloss (MD or TD) of at least 40, or 45%, or within a range from 40, or 45 to 60, or 80%.
  • the film can be formed by any known process, but is preferably formed by "blowing" in a blown film process.
  • the final film may be a single layer film comprising the polyethylene as a blend with other polymers, especially other polyolefins, or consisting essentially of the polyethylene and common additives such as antioxidants, fillers, etc.
  • the film may also comprise two, three, four, five or more layers where any one or more of the layers may comprise or consist essentially of the polyethylene.
  • a layer of the film comprises polyethylene, it may be as a blend with other polyolefins such as low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene homopolymer, polypropylene copolymer, and combinations thereof.
  • the polyethylene melt is extruded through a die such as an annular slit die, usually vertically, to form a thin walled tube.
  • Cooling preferably in the form of positive air pressure, is introduced via a device in the center of the die to blow up the tube like a balloon. Cooling can also be effectuated or assisted by other means such as external (to the film) devices, and the air may be nitrogen/oxygen or other gases or mixtures of gases or liquids.
  • a high-speed air ring blows onto the exterior of the hot film to cool it.
  • the cooling may occur at some adjustable distance from the die, which is typically at least 1 cm from the die from which the melt extrudes.
  • the tube of film can then continue upwards or away from the die in a "machine direction", continually cooling, until it may pass through nip rolls where the tube is flattened to create what is known as a "lay-flat” tube of film.
  • This lay-flat or collapsed tube can then be taken back down the extrusion "tower” via more rollers.
  • the air inside the bubble is also exchanged. This is known as IBC (Internal Bubble Cooling).
  • the ingredients used to form the film are added in any desirable form, preferably as granules, in a hopper which feeds the material to one or more extruders where the materials are melt blended at a desirable temperature through shear forces and/or heating.
  • the molten material is then fed, with or without filtering, to a die which is also heated to a desired temperature such as 180 to 220°C and then forced from the die in a direction away from the die at least in part by force of blown air.
  • the cooling of the forming film takes place as the film moves away from the die, and preferably a high-speed air ring that blows air that is at least 10 or 20°C cooler than the surrounding air facilitates that cooling.
  • the surrounding temperature in the area of the forming film is within a range from 20°C, or 30°C to 50°C, or 60°C.
  • the forming film is cylindrical and the air ring forms a ring round the cooling tube that blows air concentrically around the film.
  • the air preferably blows against the outside of the film, most preferably around the entire circumference formed by the film.
  • the distance of the device from the die opening can be made to vary to allow a "relaxation time" for the hot film to gradually cool prior to being exposed to the cooling air from the cooling device.
  • lay-flat film is then either kept as such or the edges of the lay-flat are slit off to produce two flat film sheets and wound up onto reels.
  • Articles such as bags can be made from such lay-flat films.
  • the tube of film is made into bags by sealing across the width of film and cutting or perforating to make each bag. This is performed either in line with the blown film process or at a later stage.
  • the expansion ratio between the die and blown tube of film would be 1.5 to 4 times the die diameter.
  • the drawdown between the melt wall thickness and the cooled film thickness occurs in both radial and longitudinal directions and is easily controlled by changing the volume of air inside the bubble and by altering the haul off speed. This gives blown film a better balance of properties than traditional cast or extruded film which is drawn down along the extrusion direction only.
  • the die used in the formation of the films herein is designed such that the die opening, through which the molten polyolefin extrudes, is in the form of a ring and the molten polyolefin emanating therefrom is in the form of a continuous tube.
  • the Die Factor Rate at which the film is formed is within a range from 10 lb/in-hr, or 15 to 20 lb/in- hr, or 26 lb/in-hr, or 30 lb/in-hr, or 40 lb/in-hr (0.56 kg/mm-hr, or 0.84 to 1.12 kg/mm-hr, or 1.46 kg/mm-hr, or 1.69 kg/mm-hr, or 2.25 kg/mm-hr); and preferably the Maximum Rate of extrusion is within a range from 350 lb/hr (159 kg/hr) to 500 lb/hr (227 kg/hr). Note that for the "Die Factor" there is one more difference besides the units.
  • the die dimension is the die circumference, while in the metric unit, the die dimension is the die diameter.
  • the inventive film most preferably a monolayer film comprising or consisting essentially of the polyethylene, will have many desirable properties.
  • the film has an average thickness within a range from 10, or 15 ⁇ to 40, or 60, or 80, or 100 ⁇ , most preferably from 15 to 40 ⁇ .
  • the film has a Seal Initiation Temperature (measured as described below) at IN force (°C) within a range from 80°C, or 85°C to 105°C, or 110°C, or 1 15°C.
  • the film has a Maximum Hot Tack Force (measured as described below) of greater than 10, or 12, or 13 N, or within a range from 10, or 12, or 13 N to 18, or 20 N.
  • the film has a MD Tensile Strength within a range from 7800 psi to 8,000, or 10,000 psi; and a TD Tensile Strength within a range from 6500 psi to 6500, or 8500 psi.
  • the film has an MD Elongation at Break within a range from 350 to 500%, or 600%, and a TD Elongation at Break within a range from 450 to 800 %.
  • the film has an MD Elmendorf Tear within a range from 100 to 200 g, or 250, or 300 g, and a TD Elmendorf Tear within a range from 350 to 650 g. In any embodiment, the film has an MD 1 % Secant Flexural Modulus within a range from 25 to 35 kpsi, or 40 kpsi, or 50 kpsi, and a TD 1% Secant Flexural Modulus within a range from 20 to 50 kpsi, or 60 kpsi, or 70 kpsi.
  • polyethylene or polyethylene film when the phrase "consists essentially of is used that means that the polyethylene, or film made of the polyethylene, includes less than 5, or 4, or 3, or 2, or 1 wt%, by weight of the polyethylene, or additives as are known in the art, such as fillers, colorants, antioxidants, anti- UV additives, curatives and cross-linking agents, aliphatic and/or cyclic containing oligomers or polymers, often referred to as hydrocarbon polyethylenes, and other additives well known in the art, and other common additives such as disclosed in WO 2009/007265.
  • additives such as fillers, colorants, antioxidants, anti- UV additives, curatives and cross-linking agents, aliphatic and/or cyclic containing oligomers or polymers, often referred to as hydrocarbon polyethylenes, and other additives well known in the art, and other common additives such as disclosed in WO 2009/007265.
  • polyethylenes produced by the methods outlined above.
  • the various descriptive elements and numerical ranges disclosed herein for the polyethylenes, processes and films can be combined with other descriptive elements and numerical ranges to describe the invention(s); further, for a given element, any upper numerical limit can be combined with any lower numerical limit described herein, including the examples in jurisdictions that allow such combinations.
  • the features of the inventions are demonstrated in the following non-limiting examples. The testing methods used to test the polymers and films made therefrom are also described. Test Methods
  • the catalysts precursors used in the examples that generated the exemplary poly ethylenes are as follows, and the ratios in which they are combined are weight ratios:
  • C1/C2 80:20: To a stirred vessel 1400 g of toluene was added along with 925 g of methylaluminoxane (30 wt% in toluene). To this solution 734 g of ES70 - 875°C calcined silica (Purchased from PQ Corporation and calcined to 875°C before use) was added. The reactor contents were stirred for three hours at 100°C. The temperature was then reduced and the reaction was allowed to cool to ambient temperature.
  • Dimethylsilyl(n- propylcyclopentadienide) hafnium dimethyl (11.50 g, 24.00 mmol) and bis-ethylindenyl zirconium (IV) dimethyl (2.45 g, 6.00 mmol) were then dissolved in toluene (250 g) and added to the vessel, which was allowed to stir for two more hours. The mixture was then stirred slowly and dried under vacuum for 60 hours, after which 1019 g of light yellow silica was obtained.
  • C1/C3 80:20: To a stirred vessel 1400 g of toluene was added along with 925 g of methylaluminoxane (30 wt% in toluene). To this solution 734 g of ES70 - 875°C calcined silica was added. The reactor contents were stirred for three hours at 100°C. The temperature was then reduced and the reaction was allowed to cool to ambient temperature.
  • Dimethylsilyl(n-propylcyclopentadienide) hafnium dimethyl (11.50 g, 24.00 mmol) and bis- methylindenyl zirconium (IV) dimethyl (2.28 g, 6.00 mmol) were then dissolved in toluene (250 g) and added to the vessel, which was allowed to stir for two more hours. The mixture was then stirred slowly and dried under vacuum for 60 hours, after which 1049 g of light yellow silica was obtained.
  • C1/C4 70:30: To a stirred vessel 1400 g of toluene was added along with 925 g of methylaluminoxane (30 wt% in toluene). To this solution 734 g of ES70 - 875°C calcined silica was added. The reactor contents were stirred for three hours at 100°C. The temperature was then reduced and the reaction was allowed to cool to ambient temperature.
  • Dimethylsilyl(n-propylcyclopentadienide) hafnium (IV) dimethyl (10.06 g, 21.00 mmol) and tetramethylcyclopentadienyl methylindenyl zirconium dimethyl (2.31 g, 6.00 mmol) were then dissolved in toluene (250 g) and added to the vessel, which was allowed to stir for two more hours. The mixture was then stirred slowly and dried under vacuum for 60 hours, after which 998 g of light yellow silica was obtained.
  • C1/C4 80:20: To a stirred vessel 1400 g of toluene was added along with 925 g of methylaluminoxane (30 wt% in toluene). To this solution 734 g of ES70 - 875°C calcined silica was added. The reactor contents were stirred for three hours at 100°C. The temperature was then reduced and the reaction was allowed to cool to ambient temperature.
  • the ratio of poor incorporator and good incorporator can also be used to tune the product properties. Increasing from 20 mol% to 30 mol% CI paired with C4 resulted in an MIR increase from 21 to 24.
  • 3 ⁇ 4 NMR data was collected at 393K in a 10 mm probe using a Bruker spectrometer with a 3 ⁇ 4 frequency of at least 400 MHz (available from Agilent Technologies, Santa Clara, CA). Data was recorded using a maximum pulse width of 45°C, 5 seconds between pulses and signal averaging 512 transients. Spectral signals were integrated and the number of unsaturation types per 1000 carbons was calculated by multiplying the different groups by 1000 and dividing the result by the total number of carbons. The number average molecular weight (Mn) was calculated by dividing the total number of unsaturated species into 14,000, and has units of g/mol.
  • the TCB mixture is filtered through a 0.1 ⁇ Teflon filter and degassed with an online degasser before entering the GPC instrument.
  • the nominal flow rate is 1.0 mL/min and the nominal injection volume is 200 ⁇ ⁇ .
  • the whole system including transfer lines, columns, detectors are contained in an oven maintained at 145°C.
  • Given amount of polymer sample is weighed and sealed in a standard vial with 80 flow marker (heptane) added to it.
  • polymer After loading the vial in the auto-sampler, polymer is automatically dissolved in the instrument with 8 mL added TCB solvent. The polymer is dissolved at 160°C with continuous shaking for about 1 hour for most polyethylene samples or 2 hour for polypropylene samples.
  • the TCB densities used in concentration calculation are 1.463 g/ml at room temperature and 1.284 g/ml at 145°C.
  • the sample solution concentration is from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • Values for Mn are ⁇ 2,000 g/mole, for Mw are ⁇ 5,000 g/mole, and Mz are ⁇ 50,000 g/mole.
  • the mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the predetermined concentration multiplied by injection loop volume.
  • IR MW The conventional molecular weight (IR MW) was determined by combining universal calibration relationship with the column calibration which is performed with a series of mono-dispersed polystyrene (PS) standards ranging from 700 to 10,000 kg/mole.
  • PS mono-dispersed polystyrene
  • Cross-fractionation chromatography which combines TREF and traditional GPC (TREF/GPC) as disclosed in WO 2015/123164 Al, and described in U.S.S.N. 62/350,223 filed on June 15, 2016, was performed on a CFC-2 instrument from Polymer Char, Valencia, Spain on the poly ethylenes generated as described above in Table 1.
  • the instrument was operated and subsequent data processing, for example, smoothing parameters, setting baselines, and defining integration limits, was performed according to the manner described in the CFC user manual provided with the instrument or in a manner commonly used in the art.
  • the instrument was equipped with a TREF column (stainless steel, o.d., 3/8"; length, 15 cm; packing, non-porous stainless steel micro-balls) in the first dimension and a GPC column set (3 x PLgel 10 ⁇ Mixed B column from Polymer Labs, UK) in the second dimension. Downstream from the GPC column was an infrared detector (IR4 from Polymer Char) capable of generating an absorbance signal that is proportional to the concentration of polymer in solution.
  • IR4 infrared detector
  • a temperature-gradient gel permeation chromatographic column As used throughout the claims and description, such a dual-column system will be referred to generally as a "temperature-gradient gel permeation chromatographic column", as any combination of molecular weight sensitive and temperature sensitive or branching- sensitive separation means can be employed and can include one, two, or more types of separation means such as columns through which dissolved polymer is differentially eluted.
  • the sample to be analyzed was dissolved in ortho-dichlorobenzene, at a concentration of about 5 mg/ml, by stirring at 150°C for 75 min. Then a 0.5 ml volume of the solution containing 2.5 mg of polymer was loaded in the center of the TREF column and the column temperature was reduced and stabilized at about 120°C for 30 min. The column was then cooled slowly (0.2°C/min) to 30°C (for ambient runs) or -15°C (for cryogenic runs) to crystallize the polymer on the inert support. The low temperature was held for 10 min before injecting the soluble fraction into the GPC column.
  • each fraction is listed by its fractionation temperature (Ti) along with its normalized weight percent (wt%) value (Wi), cumulative weight percent, that is, the sum weight percents in the graphs of FIG. 2 and FIG. 3, and various moments of molecular weight averages (including weight average molecular weight, Mwi).
  • FIG. 2 and FIG. 3 are plots that graphically illustrate the calculations used to determine branching within the molecular weight fractions of polyethylenes.
  • the x-axis represents the elution temperature in centigrade
  • the right hand y- axis represents the value of the integral of the weights of polymer that have been eluted up to an elution temperature.
  • the temperature at which 100% of the material has eluted in this example was about 100°C.
  • the closest point at which 50% of the polymer has eluted was determined by the integral, which was used then to divide each of the plots into a l st -half and a 2 nd -half.
  • a gradient of molecular weight fractions of the polyethylene elutes from at least one temperature-gradient gel permeation chromatographic column at a gradient of temperatures and molecular weights, where 50 wt% or less of the cumulative molecular weight polyethylene fractions elutes at a temperature T w i, and greater than 50 wt% cumulative molecular weight polyethylene fractions elute at a temperature T W 2, the molecular weight fractions eluting at T w i being a molecular weight component M w i and the fractions eluting at T W 2 being a molecular weight component M W 2.
  • the first part of the process is illustrated by FIG. 2. From the CFC data, the fraction whose cumulative weight percentage (sum weight) is closest to 50% was identified (e.g., the fraction at 84°C on FIG. 2) of the polyethylenes. The fractional CFC data was divided into two halves, for example, Ti ⁇ 84°C as the 1st half and Ti > 84°C as the 2nd half on FIG. 2. Fractions which do not have molecular weight averages reported in the original data file are excluded, for example, excluding the fractions with Ti between 25°C and 40°C on FIG. 2. [0067] In FIG. 2, the left hand y-axis represents the weight percent (wt%) of the eluted fraction. Using the procedure above to divide the curves into two halves, these values are used to calculate the weight average elution temperature for each half using the formula shown in (2):
  • Ti represents the elution temperature for each eluted fraction
  • Wi represents the normalized weight % (polymer amount) of each eluted fraction. For the example shown in FIG. 2, this provides a weight average elution temperature of 64.9°C for the first half, and 91.7°C for the second half.
  • the left hand axis represents the weight average molecular weight (Mwj) of each eluted fraction. These values are used to calculate the weight average molecular weight for each half using the formula shown in (3):
  • Mw represents the weight average molecular weight of each eluted fraction
  • Wi represents the normalized weight % (polymer amount) of each eluted fraction "i".
  • this provides a weight average molecular weight of 237,539 g/mole for the first half, and 74, 156 g/mole for the second half.
  • the values calculated using the techniques described above may be used to classify the MWD and SCBD for experimental polymers and control polymers.
  • the x-axis represents the value of the difference between the first and second weight average elution temperatures
  • compositions as expressed in FIG.s 2 and 3 can be described as follows:
  • FIG. 4 is a semi-log plot of (M w i/M W 2) as a function of (T w i - T W 2) designed to show the important differences in MWD / SCBD combination among inventive examples compared to commercial benchmarks. Such differences are believed to play a key role in determining the trade-off pattern and/or balance of various performance attributes such as stiffness, toughness and processability.
  • the polyethylenes are above the mid-horizontal line, while conventional polyethylenes having typical short-chain branching distribution (SCBD) are below the mid-line.
  • SCBD typical short-chain branching distribution
  • NSCBD narrow short chain branching distribution
  • BSCBD broad short chain branching distribution
  • the polyethylenes are in-between the extremes, represented by an Mwi/Mw2 value of between 0.9 and 10, more preferably 1.5 and 5.
  • BOCD Low Mw/High Tw
  • ⁇ LL3001 polyethylene is obtained from ExxonMobil Chemical Company (Baytown,
  • VPR is a polyethylene made in a metallocene gas phase process as described in PCT/US2015/015119 (Polymer 1 -10, Table 1).
  • EEO Energy specific output
  • rate is the extrusion output (lb/hr) in film extrusion normalized by the extruder power (hp) consumption and is a measure of a material's processability.
  • TDA is the total defect area. It is a measure of defects in a film specimen, and reported as the accumulated area of defects in square millimeters (mm 2 ) normalized by the area of film in square meters (m 2 ) examined, thus having a unit of (mm 2 /m 2 ) or "ppm” In Table 4 below, only defects with a dimension above 200 microns are reported.
  • OCS Optical Control System
  • This system consists of a small extruder (ME20 2800), cast film die, chill roll unit (Model CR-9), a winding system with good film tension control, and an on-line camera system (Model FSA-100) to examine the cast film generated for optical defects.
  • OCS Optical Control System
  • Extruder temperature setting (°C): Feed throat/Zone 1/Zone 2/Zone 3/Zone4/Die: 70/190/200/210/215/215
  • the film forming system generates a cast film of about 4.9 inch in width and a nominal gauge of 1 mil (25 ⁇ ). Melt temperature varies with materials, and is typically around 215°C.
  • the polyethylene's crystalline content can be estimated from density measurements using the following two component model (4):
  • the crystallinity of polyethylenes depends on the densities assumed for the crystalline and amorphous regions of the molecules: a pure polyethylene crystal has a gradient density of 0.999 g/cm 3 , while a completely amorphous polyethylene has a gradient density of 0.860 g/cm 3 .
  • a polyethylene's density as determined by the gradient density method is termed its "total crystallinity".
  • the polyethylenes outlined in Table 7 were also analyzed using differential scanning calorimetry employing 3-5 mg samples sealed in aluminum sample pans. Since the samples' second melt was used, no conditioning was performed. The DSC data was recorded by gradually heating the sample to 180 to 200°C at a rate of 10°C/min. The sample was kept at the maximum temperature for 5 minutes before the cooling-heating cycle was applied; both were conducted at rates of 10°C/min. The samples were cooled to at or below 40°C or cooler before being reheated. Both the first and second cycle thermal events were recorded. The melting temperature was measured and reported during the second heating cycle (or second melt). The analysis was conducted with a minimum of three replicates and the average of the three recorded.
  • the temperature at 70% Cumulative Heat Flow is an estimate for the Hot Tack Temperature (°C) of the polyethylene's film.
  • the temperature at 80% Cumulative Heat Flow is an estimate for the Heat Seal Initiation Temp (°C) of the polyethylene's film.
  • the temperature at 60% Cumulative Heat Flow is an estimate for the polyethylene's "stickiness", which is measure of the ability to produce the polyethylene in a gas phase reactor. The reactor tends to foul at temperatures above the "stickiness temperature", for instance, above 100°C or 110°C or 120°C. All three temperatures are indicators: the first two temperatures for film performance and the last temperature for reactor operability.
  • polyethylenes' crystallinity was determined using DSC methodology, the result termed the polyethylene's "core crystallinity", and is defined as follows (5):
  • Crystallinity — (5), where ⁇ 3 ⁇ 4 is the heat of fusion of the sample and AHf° is the heat of fusion of a pure polyethylene crystal (4110 J/mole).
  • AHf polyethylene's heat of fusion
  • ⁇ in J/g total heat flow
  • a polyethylene's heat of fusion being 1962.8 J/mole (140.2 J/g ⁇ 14 g/mole) corresponds to a core crystallinity of 47%.
  • the "interfacial content” is the difference between the polyethylene's crystallinity by GDC and its core crystallinity; for example 46 - 39 gives an interfacial content of 7%.
  • Density by DSC was then calculated by rearranging equation (3) and using the polyethylene's core crystallinity to determine its density. Density by DSC is for example as follows: 1 / (1.168 - 0.162 ⁇ (Mass Fraction of Core Crystallinity)). - ⁇ -
  • the inventive process produces polyethylenes that should have an improved balance of stiffness and sealing performance, that is, increased stiffness at any Hot Tack, and increased stiffness at any Heat Seal Initiation temperature, as can be deduced in these data.
  • the data also indicates the inventive polyethylenes will also have higher operability temperatures at any crystallinity (density). This new balance of crystallinity and operability temperature can open a new operating window for making gas phase polyethylenes.
  • the claimed polyethylene or polyethylene film includes only the named components and no additional components that will alter its measured properties by any more than 20%, and most preferably means that additional components are present to a level of less than 5, or 4, or 3, or 2 wt% by weight of the composition.
  • additional components can include, for example, fillers, colorants, antioxidants, anti-UV additives, curatives and cross-linking agents, aliphatic and/or cyclic containing oligomers or polymers, often referred to as hydrocarbon polyethylenes, and other additives well known in the art.
  • the phrase "consisting essentially of means that there are no other process features that will alter the claimed properties of the polyethylene and/or film produced therefrom by any more than 10 or 20%.

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Abstract

L'invention concerne un polyéthylène utile pour un film comprenant des unités dérivées d'éthylène et dans une plage de 0,5 à 20 % en poids d'unités dérivées d'alpha-oléfine en C3 à C12, une valeur d'I2 dans une plage de 0,5 à 20 g/10 min, une valeur d'I21 dans une plage de 5 à 100 g/10 min; ce polyéthylène est formé à partir d'un procédé consistant à combiner un catalyseur métallique du groupe 4 de bis-cyclopentadiényle ponté, un catalyseur métallique du groupe 4 de bis-cyclopentadiényle non ponté, et un activateur comprenant éthylène et dans une plage de 0,1 à 5 % en poids, par rapport au poids de tous les monomères, d'une alpha-oléfine en C3 à C12, à une température comprise dans une plage de 60 à 100° C.
PCT/US2017/060433 2016-12-05 2017-11-07 Polyéthylènes métallocènes à large distribution orthogonale pour films WO2018106388A1 (fr)

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CN201780083063.XA CN110167974B (zh) 2016-12-05 2017-11-07 用于膜的宽正交分布茂金属聚乙烯
MYPI2019003171A MY191910A (en) 2016-12-05 2017-11-07 Broad orthogonal distribution metallocene polyethylenes for films
BR112019011558-7A BR112019011558B1 (pt) 2016-12-05 2017-11-07 Polietilenos de metaloceno que compreende unidades derivadas de etileno, seu processo de formação e películas
EP17798368.1A EP3548525A1 (fr) 2016-12-05 2017-11-07 Polyéthylènes métallocènes à large distribution orthogonale pour films
CA3045440A CA3045440C (fr) 2016-12-05 2017-11-07 Polyethylenes metallocenes a large distribution orthogonale pour films
JP2019530059A JP7045377B2 (ja) 2016-12-05 2017-11-07 幅広い直交分布のフィルム用メタロセンポリエチレン
KR1020197016144A KR102212822B1 (ko) 2016-12-05 2017-11-07 필름용의 브로드 오쏘고날 분포 메탈로센 폴리에틸렌

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KR102272245B1 (ko) 2018-12-18 2021-07-02 한화솔루션 주식회사 올레핀 중합용 촉매 및 이를 이용하여 제조된 올레핀계 중합체
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